TW554244B - Positive type photosensitive resin composition, process for producing pattern and electronic parts - Google Patents

Abstract

Disclosed are a positive type photosensitive resin composition which comprises (A) a polyimide precursor or a polyoxazole precursor having a group represented by -OR, wherein R represents a monovalent group constituting a acetal or ketal, an alkoxyalkyl group or an alkylsilyl group, which can be converted into a hydrogen atom by decomposition with an action of an acid, in the molecule which is bonded to an aromatic ring, and (B) a compound which generates an acid by irradiating radiation, a process for producing the same and electronic parts using the same.

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 554244 5. Description of the Invention (1) [Field of Invention] The present invention relates to a heat-resistant positive-type photosensitive agent containing a photosensitive polyimide precursor or a polyoxazole precursor. Resin composition, method for manufacturing pattern, and electronic component using the same. [Background Art] For the surface protective film or interlayer insulating film of a semiconductor device, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used hitherto. However, in recent years, semiconductor devices currently require high integration and large size, but encapsulation resin packaging requires thin and small size. Therefore, a surface coating or flux reflow system such as by a LOC (Wire on Chip) has been used so that a polyimide resin having more excellent mechanical properties, heat resistance, etc. than before is eagerly desired. On the other hand, a polyimide resin having a photosensitive property by itself is used. When this material is used, there are characteristics that can simplify the pattern forming step and shorten the complicated manufacturing method. A heat-resistant photoresist including a photosensitive polyimide or a precursor thereof and uses thereof are well known in the art. For example, for negative materials, a method for introducing a methacrylfluorene group into a polyfluorene imide precursor via an ester bond or an ionic bond has been proposed (Japanese Provisional Patent Publication No. 11541/1974, 4922/1975, 145 7 94/1979, 3 803 8/1981, etc.), soluble polyfluorene imine with photopolymerizable olefins (Japanese Provisional Patent Publication Nos. 108031/1984, 220730/1984 '232122/1984' 6729/1985, 72925 / 1985, 57620/1986, etc.), self-sensitized polyimide with a benzophenone skeleton and an alkyl group at the ortho position of the aromatic ring to be bonded to the nitrogen atom (Japanese paper size is applicable to China) Standard (CNS) A4 specification (210 X 297 public love) --------- 1 --- install -------- order ----. Ϊ (Please read the precautions on the back first (Fill in this page again)

ϋ l · —I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 554244 A7 __________B7__________ V. Description of the Invention (2) Patent Publication No. 219330/1984, 231533/1984), etc.). Among the above-mentioned negative materials, an organic solvent such as N-methyl oxolidine and the like is required during development, and in recent years, a positive-type photosensitive resin capable of being developed by an alkaline aqueous solution has been proposed so far. For positive materials, a method for introducing o-nitrobenzyl into a polyimide precursor via an ester bond has been proposed (Journal of Macromolecular Science and Chemistry, A24, 10, 1407, 1987), mixed naphthoquinone azide Method for compound and soluble hydroxyimide or polyoxazole precursor (Japanese Patent Publication No. 60630/1989, U.S. Patent No. 4,395,482), introducing naphthalene diazide compound into soluble polyfluorene imide via a bond Method (macromolecule, 23, 1990), chemically amplified polyfluorene imide (Japanese Provisional Patent Publication No. 763/1995), a material in which naphthoquinone diazide and polyfluorene imide precursor are mixed (Japan Provisional Patent Publication No. 13315/1977), a method using an acid generator and a polyamidate or a polyphenol (in which the pendant group is protected by an alkoxycarbonyl group) (Japanese Provisional Patent Publication No. 02489 / 1999) and so on. However, in the above-mentioned negative materials, there is a problem in that the function and resolution of the negative materials and the yield of the negative materials decrease. Moreover, among the above materials, the structure of the polymer to be used is limited, so that the physical properties of the finally obtained film material are also limited, making it unsuitable for multi-purpose applications. On the other hand, in the positive type material, there is a similar problem that the sensitivity or resolution is low due to problems associated with the absorption wavelength of the photosensitizer as described above, or its structure is limited. In addition, among the above-mentioned materials, there are problems because the thickness of the film material is reduced due to the high-temperature processing after the image formation, or the shape of the pattern is deteriorated due to the action of the basic components present in a small amount in the air. -* ^ ^ -------- ^ ------- r _ (Please read the precautions on the back before filling in this page) This paper standard outlines the family standard (CNS) A4 specification (210 X 297 public hair ^ 2 311837 554244 A7 -------- B7____ V. Description of the invention (3) ~ ', there is this 5 diazonaphthoquinone compound and polybenzoxazone precursor material (Japan temporarily Patent Publication No. 46: Simplified or introduced 酴 hydroxyl instead of acid, such as those who introduce the desired part into the polyamino acid through the bond, but these materials are insufficient and the thickness of the film in the unexposed part is reduced or occurs. The case where the resin is peeled from the substrate. In order to improve the developability or adhesive properties of the material, a polyamic acid material having a sintering structure in the polymer skeleton has been proposed (Japanese Provisional Patent Publication No. 31861/1992 and No. 46345/1992), Renqi 3 has polyamidic acid, which results in poor storage stability as described above. In addition, suitable materials use diazonium compounds containing many aromatic rings as acid generators, which causes heat. The problem that the mechanical properties deteriorate significantly after curing, making it unusable as a practically applicable material. None of the materials can be practically used. [Summary of the Invention] The present invention is based on the preparation of protective groups in polyimide precursors or polybenzoxazole precursors (wherein alkali-soluble groups The precursor or polybenzoxazole precursor is irradiated with radiation to protect the compound from the elimination reaction under acidic conditions), and provides a heat-resistant positive photosensitivity that can solve the above problems held by conventional photoresists. Resin composition, which can fully withstand any polyimide precursor or polybenzoxazole precursor that provides photosensitivity, and has good photosensitivity and resolution, and is rarely affected by small amounts. The effect of the amount of the basic components present in the air. 'The present invention provides a pattern which can be developed in an alkaline aqueous solution' and has excellent photosensitivity, resolution and heat resistance, and (Please read the Please fill in this page for the matters needing attention) Packing -------- Order ---- * --- 丨 Printed by the Intellectual Property Bureau Staff Consumption Cooperative of the Ministry of Economics This paper is in accordance with China National Standard (CNS) A4 (210 x 297 mm) 3 311837 554244

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The present invention also provides an electronic component having high reliability by having a pattern having a good shape and characteristics. The present invention relates to the following. 1) A positive-type photosensitive resin composition comprising (A) a polyimide precursor or a polymouth precursor having a group represented by _0R bonded to an aromatic ring in a knife, [ In the formula, a monovalent group, an alkoxyalkyl group, or an alkynyl group constituting an acetal or a ketal is shown, which can be decomposed by an acid to be converted into a hydrogen atom], and (B) an acid is generated by irradiation of radiation Of compounds. 2) The positive-type photosensitive resin composition as described above, wherein the component (A) is a polyimide precursor having a structural unit represented by the formula (1):

[Wherein R1 and R2 each represent a tetravalent organic group; each R3 represents a monovalent organic group; each R4 represents a monovalent group constituting an acetal or ketal, an alkoxyalkyl group or an alkylsilyl group, which may be Decomposed by the action of acid and converted into hydrogen atom]. 3) The positive-type photosensitive resin composition as defined above, wherein the content of (B) the compound that generates an acid by irradiation with radiation is from 0.01 to 50% by weight based on 100 parts by weight of (A) a polyimide precursor. Serving. --------- i --- install -------- order ----------- line (please read the precautions on the back before filling this page) Standards apply to China National Standard (CNS) A4 specifications (210 X 297 mm) 4 311837 311837 554244 A7 V. Description of the invention (1 4) Positive photosensitive resin composition as defined above, where

R1 is a chemical group having an aromatic group substituted by the son of 2 * 仏 ^ ^ "Bu Zhenzi Lei,", Ό 土 土, or a fluorinated alkyl group in the aromatic group having four bonded arms. 5) Positive photosensitive resin composition as defined above, wherein in formula ^), R is an aromatic group having four bonding arms or a bonding hand = an aromatic group adjacent to each other by an ether bond In the invention, a tetravalent group having a chemical structure given by an aprotic electron is substituted: a tetravalent group derived from a chemical structure of a substituted aromatic group. 6) A positive-type photosensitive resin composition as defined above, wherein the component has the following formula (2): Polyoxazole precursor of the structural unit ... (2) [wherein R5 is not a divalent organic group; R6 is a tetravalent organic group, and each R7 represents a monovalent group or an alkoxyalkane constituting an acetal or a fluorene. Radical or radical; radical which can be decomposed into hydrogen atoms by decomposition by the action of acid. 7) A positive photosensitive resin composition as defined above, in which the content is based on ⑼ wt. ) The content of the compound that generates an acid by light irradiation is 0.01 to 50 parts by weight. Mouth 8)-A kind of manufacturing pattern The method includes the following steps: a step of applying a positive photosensitive resin composition as defined above on a support and drying it, and a step of exposing, using alkali pine, 々 & ^ using an alkaline aqueous solution to expose the exposed material Steps of development and steps of heat treatment. 9) It has a pattern prepared by the above method as a surface protection film or the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297)

^ ^ M ------- β --------- (Please read the precautions on the back before filling this page) Line 0- ·

554244 V. Description of the invention u) Electronic components of interlayer insulation pimple [Simplified description of drawings] Figures 1 (a) to J (e) are diagrams showing the manufacturing steps of a semiconductor device with a multilayer wiring structure. [Description of Preferred Specific Examples] The present invention will be described in detail below. In the present invention, the component (A) is a polyfluorene imide precursor or a polyoxazole precursor and it must basically have a middle group bonded to an aromatic group (where R represents a monovalent group constituting a condensation or a ketal). , Alkoxy group or alkoxide group (which can be converted into hydrogen atoms by decomposition by the action of acid). The above-mentioned R is decomposed by the action of an acid to be converted into a hydrogen atom, thereby generating a phenolic hydroxyl group, thereby providing a suitable alkali solubility to the composition of the present invention. This group may exist in polyimide precursors, tetracarboxylic acid residues, diamine residues, or side chains, etc., and each structural unit of polyimide precursors (that is, contains a tetracarboxylic acid Residue and a repeating unit of a diamine residue), the number of the group contained is preferably 2 or more, more preferably 2 to 4. Also, this group may exist in a polyoxazole precursor, a dicarboxylic acid residue, a diamine residue, or a side bond, and the structural unit of each polyoxazole precursor (that is, contains a dicarboxylic acid Residues and a repeating unit of a dihydroxydiamine residue), the number of this group is preferably 2 or more, more preferably 2 to 4. As for the monovalent group constituting the condensation or ketal which can be converted into hydrogen atoms by decomposition by the action of acid, for example, those with the following structure can be mentioned: (Please read the precautions on the back before filling this page)

--- IIII Order --- ------III Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 6 311837 554244 A7 B7 V. Invention Note (7) g0R,! R 'means Lu and where' R, R, and R each represent an alkyl group having 5 or fewer carbon atoms, and X represents 3 or more carbon atoms (preferably A divalent alkylene group (which may have a side chain) of 20 or less carbon atoms). More specifically, tetrahydropyranyl, tetrahydrofuranyl, alkyl-substituted tetrahydropyranyl, alkyl-substituted tetrahydrofuranyl, alkoxy-substituted tetrahydropyranyl, Alkoxy-substituted tetrahydrofuranyl and the like, but the present invention is not limited to these. The most preferred group is tetrahydropyranyl. The monovalent alkoxyalkyl group or alkylsilyl group which can be converted into a hydrogen atom by decomposition by the action of an acid is not particularly limited, and the preferred carbon number of the alkoxyalkyl group is 2 to 5. The preferred carbon number is 1 to 20. More specifically, methoxymethyl, ethoxymethyl, isopropoxymethyl, tertiary butoxymethyl, ethoxyethyl, methylsilyl, ethylsilane And the like, but the present invention is not limited to these. The most preferred groups are ethoxymethyl and third butyldimethylsilyl. When the component (A) is a polyimide precursor, its structure is not particularly limited, but a polyimide precursor having a structural unit represented by the above formula (1) is preferred because it is in i -The transparency of the line region, the solubility in the alkali developer when the group shown by R4 is converted into rhenium, and the adhesion to the substrate are very excellent. This paper size applies to China National Standard (CNS) A4 specifications (21〇χ 297 issued) 7 311837 (Please read the precautions on the back before filling out this page) Loading -------- Order ----- ----- Line j Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 554244 A7 ----------- B7___ V. Outline of Invention ") ~ " "-Also, when the component (A) is a polyoxazole precursor, the structure is not particularly limited, and a polyfluorene precursor having a structural unit shown in the above formula (i) is preferred. This is because it is in i 'The transparency of the line region, when the group shown by r3 is converted into rhenium, is excellent in the solubility in the developer, and the adhesion to the substrate is very good. The polyimide precursor is explained in detail below first. In the polyfluorene imide precursor, in the structural unit represented by the formula (1), ... can be explicitly mentioned, for example, having a skeleton such as benzene, naphthalene, fluorene, biphenyl, diphenyl ether, diphenyl maple, and diphenyl. Tetravalent aromatic hydrocarbon residues such as propane, diphenylhexafluoropropane, benzophenone, etc., tetravalent fluorene group hydrocarbon residues with skeletons such as butane, cyclobutane However, the present invention is not limited to these. Its carbon number is preferably 4 to 30. Its preferred examples are phenyl, biphenyl, diphenyl bond, and diphenyl hexadecane. Incidentally: if necessary A group containing two or more of the above examples is used as R1 in the polyamino acid derivative molecule. R2 in the structural unit represented by the formula (1) can be explicitly mentioned as having, for example, a skeleton such as diphenyl ether, diphenyl ether, or diphenyl ether. Tetravalent aromatic hydrocarbon residues of phenylsulfide, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenylarsine, diphenyl maple, biphenyl, benzene, etc., but The present invention is not limited to these. Its carbon number is preferably 6 to 30. Its preferred examples are diphenylhexafluoropropane, diphenyl ether, and biphenyl. Incidentally, it may contain two or more if necessary One of the above-exemplified groups is R2. R3 in the structural unit represented by the formula (1) can explicitly mention, for example, an aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl Base, third butyl, phenyl, benzyl, etc .; have 2 to 10 carbon atoms (please read the precautions on the back before filling this page)

The size of this paper is based on Chinese National Standard (CNS) A4 (210 X 297) 8 311837 D4244

V. Description of the invention (9 '

(4) The Ministry of Economic Affairs and Intellectual Property Bureau, a hydroxyalkyl group such as methoxyethyl, etc., but the present invention is not limited to these. Among them, isopropyl and benzyl are preferred. ~ R4 in the structural unit not included in the Yiyi formula is a mono-, oxy-, or thio-alkynyl group constituting an acetal or acetal, which can be decomposed by the action of an acid to be converted into a hydrogen atom. R is the same. A polyimide precursor represented by the formula (1) in the present invention can be obtained as a part of the following formula (3), a tetrahydroacid monoacid and a diamine compound represented by the following formula (4). Made of starting materials. · (3) [wherein 'R1 has the same meaning as defined in the formula]

HVOH H2〆, ΝΗ2 [wherein 'R2 has the same meaning as defined in formula]]. The polyfluorene imide precursor can be obtained according to, for example, the following method. That is, in the presence of a suitable catalyst, such as hydrazine, etc., the tetra-s-dicarboxylic anhydride represented by the above formula (3) and the alcohol or phenol represented by the following formula (5) in an organic solvent such as N-methyl Reactions in pyrrolidone, r-butyrolactone, N, N-dimethylacetamidine, diazepam, etc. I ---- l · --- ^ ------ II Order ----- ---— Huihui (Please read the notes on the back before filling out this page} Printed by Consumer Cooperative

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, W4244 5. Description of the Invention (10): Base: tertiary butyl, phenyl, benzyl, etc .; has 2 to 10 carbon atoms, such as methoxy. Ethyl and the like, but the present invention is not limited to these. Eight, preferably isopropyl and benzyl. Then, using a toothing agent such as a part of thionyl chloride and a toothing acid, and then; in the above-mentioned organic solvent, in the presence of a suitable catalyst such as osmium, etc., the resulting compound is formulated W ^ The diamine-based compound of formula (4) reacts. The polyimide precursor obtained by the above method is crystallized in a poor solvent such as water, methanol, ethanol, propanol, propylene residue, etc., and is collected by drying and then dried. Then, in an aprotic organic solvent such as tetrahydrofuran, N-methyl «Luoge, pudding vinegar, N, N-dimethyl ethyl amine, dimethyl isocyanate, etc., the obtained material is added with a radical having R4. If necessary, the reaction catalyst performs a protective reaction to obtain a polyimide precursor having a structural unit represented by the formula (I). In the composition of the present invention, in order to make it suitable for the conventional line exposure, it is preferable to improve the transparency of the resin in the kernel line area. For the purpose of the above formula (3), R1 in the structural unit is preferably a chemical having an aromatic group substituted with an aproton-donating group or a fluorinated alkyl group in an aromatic group having four bonded arms. Structure of the quadrivalent base. In addition, R2 in the structural unit represented by formula (4) is preferably an aromatic group having four bonding arms or an aromatic group I having four bonding arms and being adjacent to each other via a bond. A tetravalent group giving the chemical structure of the aromatic group to which I is substituted. As for the specific example of the above-mentioned carboxylic acid dianhydride having a chemical structure of an aromatic group substituted with an aprotic electron donating group, it can be explicitly mentioned, for example, ^ -------- order ----- 丨 1 line. (Please (Please read the notes on the back before filling this page) 554244 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs V. Invention Description (U) 3,3 ', 4,4', _ diphenyl ether tetracarboxylic acid anhydride, 1,4-dimethoxy-2,3,5,6_benzenetetracarboxylic acid dianhydride, 1,4-bis (trimethylsilyl) -2,3,5,6-benzenetetracarboxylic acid di Acid anhydride, 1,4 · bis (3,4-dicarboxyphenoxy) phthalic anhydride, Hiromi bispyrene, 'di-undylphenoxy) phthalic anhydride, 3,3', 4,4 ,, _ Diphenylmethanetetracarboxylic dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilanic anhydride, bis (3,4-dicarboxyphenoxy) methylamine dianhydride, 4,4 '-Bis (3,4-dicarboxyphenoxy) diphenylsalfinic anhydride and the like are particularly preferably 3,3', 4,4 ',-diphenyl-tetraene dicarboxylic anhydride. Here, the electron donating group refers to a substituent having a negative value in the σρ or crm value of the Hammett-related rule. The rules and values are well known, for example, the Handbook of Chemistry, Basic Edition II, item 365 (edited by the Chemical Society of Japan, published by Maruzen, Japanese, 1984). Also, as for the chemical structure with a fluorinated alkyl group, Preferred specific examples of the carboxylic acid dianhydride include, for example, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) • Trifluoroanhydride and the like, particularly preferred is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane diacid liver. Further, as a preferable specific example of the diamine-based compound having a chemical structure of an aromatic group substituted with an aprotic electron donating group, for example, the above-mentioned R2 is benzophenone, diphenylhydrazone, diphenylarylene, Diphenylhexafluoropropane, bis (trifluoromethyl) biphenyl and other compounds. In the sulfonium imine of the present invention having the structural unit represented by the formula (1), other structural units than the structural unit represented by the formula (1) may be contained within a range that does not impair the effect of the present invention. There is no particular restriction on the molecular weight of the polyimide precursors that do not contain (A). The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297). 11 311837 --------- r --- install -------- order ---------- (Please read the precautions on the back before filling this page) 554244 A7 V. Description of the invention (u) It is preferably 10,000 to 20,000 weight average molecular weight. Incidentally, this molecular weight is measured by GPC (gel permeation chromatography) and then calculated based on polystyrene having a standard molecular weight. Next, the polyoxazole precursor is explained in detail. In the polyoxazole precursor, R5 in the structural unit represented by the formula (2) can explicitly mention, for example, that it has a skeleton such as benzyl, naphthalene, fluorene, biphenyl, diphenyl ether, diphenylene, diphenylpropane, Dibenzyl hexafluoropropane, dibenzidine, and the like are dicompensated aromatic hydrocarbon residues, or divalent aliphatic hydrocarbon residues having a skeleton such as butane, cyclobutane, and the like, but the present invention is not limited to these. Its carbon number is preferably 4 to 30. Preferred examples are phenyl, biphenyl, diphenyl ether and diphenyl hexafluoropropane. Incidentally, R5 in a molecule which may contain two or more of the above-exemplified groups as a polyamine derivative if necessary. R6 in the structural unit represented by the formula (2) can explicitly mention, for example, that it has a skeleton such as dibenzyl ether, diphenyl sulfide, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoro Tetravalent aromatic hydrocarbon residues such as propane, diphenylamidine, diphenylarsine, biphenyl, benzene, etc., but the present invention is not limited to these. Its carbon number is preferably from 6 to 30. Preferred examples thereof are diphenylhexafluoropropane, diphenyl ether and biphenyl. Incidentally, it is possible to contain two or more of the above-exemplified groups as R6 if necessary. R7 in the structural unit represented by the formula (2) is a monovalent group, an alkoxy group, or a xylyl group, which constitutes an acetal or an acetal, and its hydrazone is converted into a hydrogen atom by an acid, and is the same as the above R is the same. The substitution ratio of the protective group represented by R7 of the hydrogen atom is preferably i 〇 to the paper size. Applicable to China National Standard (CNS) A4 (210 X 297 mm) 12 311837 (Please read the precautions on the back before filling this page ) Packing -------- Order ----.------ Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554244 A7 B7 V. Invention Description (13 80%, preferably 30) To 60%. If the substitution ratio is higher than that of the upper material, the adhesiveness will sometimes decrease, and if lower than the above, the dragon will adversely affect the substrate. For example, in the present invention, the The oxazole precursor can be made by using the following carboxylic acid; 5 nr bucket / α, two made by eight (6) ^ and a diamine compound shown by the following formula 作为 as a partial starting material (6)

HO ^^ R5y / ^ 〇H

[In the formula, 'R5 has the same meaning as r5 in formula (2)]. Specific examples of the dicarboxylic acid represented by the formula (6) may include, for example, 44, dicarboxydiphenyl ether, phthalic acid, isophthalic acid, terephthalic acid, etc., a compound thereof, and at least two of the above compounds Copolymer. , &Amp; (7) (Please read the notes on the back before filling this page)

HO OH \ ϊβ η2ν〆 'νη2 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [where, R6 has the same meaning as R6 in (2)]. Specific examples of the diamine-based compound represented by the formula (7) may include, for example, 2,2f-bis (3-amino_4-hydroxyphenyl) hexafluoropropane, 4,4, _diamino_3 3, _Dihydroxy dibenzyl and the like. The polyoxazole precursor can be obtained according to the following method, for example. That is, the dicarboxylic acid represented by the formula (6) is used in an organic solvent such as methyl holodamine, r.butyrolactone, N, N-dimethylacetamide, dimethyl acer, etc. Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 13 311837 554244 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (14 Halogenating agents such as thionyl chloride, #, Then, in the same organic solvent as above, the obtained compound is reacted with a diamine compound represented by the formula (7) in the presence of a suitable catalyst such as pyridine and the like. Obtained by the above method The precursors of polyammonium chloride are crystallized in poor solvents such as methanol, ethanol, propanol, propane, etc., collected by filtration, and dried again. Then, in an aprotic organic solvent such as Siqifu, n_ Jiafu Oh, slightly burned ravioli, pudding vinegar, N, N-dimethyl ethyl amine, dimethyl isocyanate, etc., by adding a protective agent having a radical of R7 to the obtained material, and if necessary, a reaction catalyst To obtain a polyimide precursor having a structural unit represented by the above formula (I). The noise-cancelling precursor having the structural unit represented by the above formula (2) may contain structural units other than the structural unit represented by the formula (⑺). In this case, the ratio is preferably %% of all constituent units. Ear. / ❶ or less. The molecular weight of the polyoxazole precursor of the component (A) is not particularly limited, but preferably 10,000 to 200,000 weight average molecular weight. Incidentally, the molecular weight is determined by GPC (gel permeation chromatography) ) The measurement is based on polystyrene with a standard molecular weight. The knife is attached and lifted. A mixture of a polyimide precursor and a polychrysene precursor can be used as the component (A). In the composition of the present invention, the As a component of a polyimide precursor or a polyoxazole precursor, a compound that generates an acid by irradiating radiation as a component (B) (hereinafter referred to as "acid generator") is used. Photosensitivity and resolution during exposure, based on 100 parts by weight of component (a) '" ^ Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) (Please read the precautions on the back first (Fill in this page again)

Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 554244 --------- R7_ V. Description of the invention (l5) The amount of knife (B) is preferably 0.001 to 50 parts by weight, more preferably 〇01 It is particularly preferably 5 to 15 parts by weight to 20 parts by weight. The acid generator (B) used in the present invention exhibits no acidic properties when irradiated with active light such as UV light, and has a function of eliminating a protective group of a polyimide precursor or a polyoxazole hydrazone. As for the compounds of the components, for example, diarylsulfonium salts, triarylsulfonium salts, dialkylphenethylsulfonium salts, monoaryliodophosphonium salts, aryldiazophosphonium salts, aromatic tetracarboxylic acids can be explicitly mentioned. Acid salts, aromatic sulfonates, nitrobenzyl esters, aromatic N-oxyiminosulfonates, aromatic sulfonamides, naphthoquinonediazide-4-sulfonates, and the like. These compounds may be used alone or in combination of two or more kinds, or in combination with other sensitizers, as required. Among them, aromatic] oxyimino sulfonate is preferred because of the expected photosensitivity, and diaryl iodogun salts are also preferred because it is expected to have suitable properties in unexposed areas. Its dissolution prevention effect. If necessary, a tackifier such as an organosilicon compound, a silane coupling agent, a leveling agent, and the like can be added to the positive photosensitive resin composition of the present invention to impart tacky properties. Such reagents can be mentioned, for example, aminopropyltrimethoxysilane, r-aminopropyltriethoxysilane, vinyltriethoxysilane, r-glycidoxypropyltriethoxy Silane, dimethacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, ginseng (acetamidine) aluminum, aluminum acetate diisopropoxide and the like. When an adhesive property imparting agent is used, the amount thereof is preferably from 0.01 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight based on 00 parts by weight of the polyimide precursor and / or the polyoxazole precursor. Serving. --------- i ---- install -------- order ----------- (Please read the precautions on the back before filling this page) Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 15 311837 554244 A7 B7 V. Description of the invention (16) In the present invention, these ingredients are dissolved in a solvent and then used in a varnished state. As for the solvent, there can be mentioned, for example, N_methyl_24-pyrrolidone, bupropionone, (please read the precautions on the back before filling this page) N, N_ monomethylacetamide, dimethylalanine , 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, Butyl lactate, methyl-1,3-butanediol acetate, ι, 3-butanediol acetate, cyclohexanone, pentamidine, tetramethylfuran, etc., and they can be used alone or in combination of two or Use more. The amount of the solvent to be used is not particularly limited, and the amount may be generally 40 to 75% by weight based on the total weight of the composition. Method for printing a pattern using the positive photosensitive resin composition of the present invention by an employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs' by first coating the composition on a suitable support such as silicon wafer, ceramic, aluminum substrate, etc. . As for the coating method, for example, spin coating, spray coating using a mouth spray coater, dipping, printing, cylinder coating, and the like can be mentioned. Secondly, the coating film is dried by pre-baking at 60 to 120 ° C, and then irradiated with radiation or actinic radiation having a pattern having a desired shape. As for radiation or actinic radiation, X-ray, electron light, UV light, visible light, etc. can be used, and those having a wavelength of 200 nm to 500 nm are preferred. Can also use monochromatic light such as Bu line, i_ line and so on. Secondly, it is preferable to heat the exposure material to 50 to 150 ° C to diffuse the acid generated on the surface layer of the irradiated portion to the bottom portion. Then, the developing material is developed to dissolve and remove the exposed portion, so that a pattern can be obtained. As for the developer, an alkaline aqueous solution containing, for example, an inorganic base such as sodium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, etc. can be mentioned; this paper standard applies to the Zhongguanjia Standard (CNS) A4 specifications (21G X 297 public love) 16 311837 554244 A7 __________ B7 V. Description of the invention (17) (Please read the notes on the back before filling this page) Primary amines such as ethylamine and n-propylamine; secondary amines such as two Ethylamine, di-n-propylamine, etc .; tertiary amines such as triethylamine, methyldiethylamine, etc .; alcohol amines such as dimethylethanolamine, triethanolamine, etc .; quaternary ammonium salts such as tetramethylammonium hydroxide, tetrahydroxide Ethyl ammonium, etc .; and an aqueous solution containing a water-soluble organic solvent or a surfactant added to the above-mentioned alkaline aqueous solution in a suitable amount. As for the development method, a spray, paddle, impregnation, ultrasonic, etc. system can be used. Second, the pattern formed by development can be developed. As the rinse solution, distilled water can be used. Next, heat treatment is performed to obtain a final pattern having excellent heat resistance. The heat treatment temperature is usually 150 to 45 ° C. The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices or multilayer wiring boards, and more specifically, it can be used for forming a surface protective film of a semiconductor device or Interlayer insulating film, or interlayer insulating film of multilayer wiring board, etc. The semiconductor device according to the present invention is not particularly limited, as long as a surface protective film or an interlayer insulating film is provided by using the above composition of the present invention, and can be used Various structures. An example of a method for manufacturing a semiconductor device according to the present invention will be described below. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 1 is a diagram showing the manufacturing steps of a semiconductor device with a multilayer wiring structure. In the invention, a protective film 2 such as a silicon oxide film is coated on a semiconductor substrate 1 such as a Si substrate having a circuit element, and a first conductive layer 3 is formed on the exposed circuit element in addition to a predetermined portion of the circuit element. On the semiconductor substrate, an intermediate layer insulating film 4 is formed by a spin coating method (step ⑷). Next, the intermediate layer is formed on the intermediate layer. A photosensitive resin layer is formed on the insulating film 4 The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 meals) 17 311837 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554244 A7-B7 V. Description of the invention ( 18) Such as a gaseous rubber type, a novolac type, etc., and then a window 6A is formed by a conventional etching technique to expose a predetermined portion of the interlayer insulating film 4 (step y (b)). Use a gas such as oxygen, Carbon fluoride or the like selectively etches the interlayer insulating film 4 of the window 6A by dry etching to open the window 6B. Then, only the photosensitive resin layer 5 is engraved without etching the first exposed portion of the window 6B. The etching solution of a conductive layer 3 completely removes the photosensitive resin layer 5 (step (c)). Then, the second conductive layer 7 is formed using a conventional technique to completely perform the electrical connection with the first conductive layer 3 (step (D)). When it is desired to form a multilayer wiring structure of three or more layers, the above steps are repeatedly performed to form individual layers. Next, 'the surface protection film 8 is formed. In the example of this figure, spin coating is used. Method for coating the above photosensitive tree The composition is dried and then irradiated with light to form a photomask forming a pattern of a predetermined portion of the window 6C, and then developed by an alkaline aqueous solution to form a pattern, and then heated to form a resin film to form a surface protective film 8. This resin film It is used to protect the conductive layer from external stress, alpha rays, etc., so that the obtained semiconductor device has excellent reliability. Incidentally, in the above examples, it is also possible to use the photosensitive resin composition of the present invention to form an intermediate layer. Insulating film. [Examples] Hereinafter, the present invention will be described in more detail with reference to examples. FExample 1 Synthesis of Caprylic Acid Vinegar (Please read the note on the back? Matters before filling out this page}

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 18 311837 554244 A7 _____B7____ V. Description of the invention (1S >) 10 grams of 3,3 ', 4,4'-diphenyl ether tetracarboxylate Acid diacid anhydride (〇dpa) and 3.87 g of isopropanol were dissolved in 45 g of N'N · dimethylacetamide (DMAc), and then a catalytic amount of 1,8-diazabicyclo [5 · 4 · 0] Undecene, the mixture was heated at 60 ° C. for 2 hours, and then stirred at room temperature for 15 hours to carry out the esterification reaction. After that, 7.1 g of vaporized thionine was added to the mixture under ice-cooling, and the resulting mixture was returned to room temperature and allowed to react for 2 hours. Then, 10.6 g of 2,2-bis (3-amino_4-hydroxyphenyl) hexafluoropropane and 4 67 g of pyridine dissolved in 45 g of DMAc were added to the above mixture under ice-cooling to make the mixture Stir at room temperature for 30 minutes. This reaction mixture was added dropwise to distilled water, and then Shen Dianwu was collected by filtration, and dried under reduced pressure to obtain polyurethane. This material has a weight average molecular weight of 24,000 and a number average molecular weight of 17,000. The spectrum of the hydroxyl group was tested, and 10 g of the polyamidate obtained above was dissolved in 50 g of tetrahydrofuran, and 26 g of 2,3-dihydropyran and a catalytic amount of p-toluenesulfonic acid were added to the solution. The mixture was stirred at room temperature for 1 hour. This reaction mixture was added dropwise to distilled water, and the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor represented by the formula (1). The substitution ratio of the tetrahydropyranyl group to the vial of the obtained material was 54%. Evaluation of photosensitive characteristics: 100 parts by weight of the foregoing polyimide precursor was added with 15 parts by weight of dimethoxyanthracenesulfonate diphenyliodide as a compound that generates an acid by light irradiation, and the mixture was dissolved in 2 _ methoxyethanol. (Please read the precautions on the back before filling out this page.) -------- Order ---------- Line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Guan Family Standard (CNS) A4 specification (210 X 297 public love) 19 311837 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554244 A7 ----- B7 V. Description of the invention (2) The above on a silicon wafer The solution was spin-coated to form a coating film with a dry film thickness of 2 to 3 microns, and then subjected to i-line (365 nm) exposure through an interference filter using an ultra-high pressure mercury lamp. After the exposure, the exposed material was heated at 90 ° C for 5 minutes, and developed with a mixed solution (volume ratio 5: 1) of 2.38 wt% tetramethylammonium hydroxide aqueous solution and methanol until the silicon wafer was exposed at the exposed portion. . As a result, a good pattern having a resolution of 10 m and a film residual rate of 90% on the unexposed portion was obtained. The exposure dose at this time was 200 microjoules per square millimeter. Note that even after 'exposure', even if the material is left to stand for 3 () minutes to 2 hours before the heating step, no deterioration in the shape of the pattern is observed. Example 2 In the same manner as in Example 1, except that the tetracarboxylic dianhydride used in Example 1 was changed to 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 'to synthesize polyfluorene The imine precursor (weight-average molecular weight: 14,500, number-average molecular weight: 11,000) was subjected to evaluation of photosensitivity characteristics in the same manner as in Example i. As a result, a good pattern having a resolution of 6 micrometers and a film residual rate of 92% in the unexposed portion was obtained. The exposure dose at this time was 200 microjoules per square millimeter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration in the shape of the pattern was observed. Example 3 In Example 1, a compound that generates an acid by irradiation with radiation was changed to naphthalenedimethyliminotrifluoromethanesulfonic acid and a 2 wt% 0/0 tetramethylammonium hydroxide aqueous solution was used as a developer to Example 丨 Feel the same way -------- r --- install -------- order ----- (Please read the precautions on the back before filling this page) 0 copies The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 20 311837 554244 A7 ------ B7 V. Description of the invention (21) Evaluation of optical properties. As a result, a good pattern having a resolution of 8 micrometers and a film residual rate of 92.0 / 0 in the unexposed portion can be obtained. The exposure dose at this time (please read the precautions on the back before filling this page) is 150 microjoules per square millimeter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration in the shape of the pattern was observed. Example 4 In Example 2, the compound that generates an acid by irradiating was changed to naphthalene dimethyl iminotrifluoromethanesulfonic acid and a 2 38 wt% 0 / 〇 氲 aqueous solution of tetramethyl money was used as a developer. Evaluation of photosensitivity characteristics was performed in the same manner as in Example 1. As a result, a good pattern having a resolution of 8 micrometers and a film residual ratio of 90/0 to the unexposed portion can be obtained. The exposure dose at this time was 100 microjoules per square millimeter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration in the shape of the pattern was observed. Reemployment Example 5 Polyammonium Ethyl Essence of Fen # Dissolve 10 g of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride in 45 g of N, N-dimethylacetamide (DmAc) (〇dPa) and 3.87 grams of isopropyl alcohol, printed in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, added a catalytic amount of 1,8-diazabicyclo [5 · 40] undecene, and made this mixture It was heated at 60 ° C for 2 hours, and then stirred at room temperature for 15 hours to carry out the esterification reaction. Thereafter, 7.1 g of vaporized thionine was added to the mixture under ice-cooling, and the resulting mixture was returned to room temperature and allowed to react for 2 hours. Then, under ice cooling, 10.6 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4 67 g of pyridine dissolved in 45 g of DM Ac were added to the above mixed paper. National Standard (CNS) A4 Specification (210 X 297 Meals) 21 311837 554244 A7 V. Description of Invention (22) (Please read the note on the back? Matters before filling out this page) and then stir the mixture at room temperature. minute. This reaction mixture was added dropwise to distilled water, and the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyurethane. This material has a weight average molecular weight of 24,000 and a number average molecular weight of 17,000. Dissolve 10% of the polyamic acid vinegar obtained above in 50 g of butyrolactone. Then, put 1.96 g of tert-butyldimethylsilyl silane into this solution, and cool under ice This mixture was stirred for 3 hours. This reaction mixture was added dropwise to distilled water, and the formed precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor represented by the formula (1). The substitution ratio of the third butyl dimethyl apatite group to the hydroxyl group of the obtained material was 46%. Evaluation of photosensitivity characteristics: 100 parts by weight of the foregoing polyimide precursor was added with 15 parts by weight of a dimethoxyanthracenesulfonic acid diphenyliodine gun as a compound that generates an acid by irradiation with radiation, and this mixture was dissolved in 2 -Methoxyethanol. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed on the Xixi wafer to apply spin coating to the above solution to form a coating film with a dry film thickness of 2 to 3 microns, and then performed the interference filter using an ultra-high pressure mercury lamp. i-line (365 nm) exposure. After exposure, the exposed material was heated at 10 CTC for 5 minutes, and developed with a mixed solution (volume ratio 5: 1) of 2.38 wt% tetramethylammonium hydroxide aqueous solution and methanol until exposed on the exposed silicon wafer. Rinse it with water. As a result, a good pattern having a resolution of 15 micrometers and a film residual ratio of 88% on the unexposed portion was obtained. The exposure dose at this time was 25 microjoules per square millimeter. Incidentally, after exposure, even before the heating step, make this paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 22 311837 554244 A7 ------ B7 V. Description of the invention (23 ) No deterioration in pattern shape was observed even after the material was left to stand for 30 minutes to 2 hours. Example 6 (Please read the precautions on the back before filling this page) In the same way as in Example 5, but the tetracarboxylic acid dianhydride used in Example 5 was changed to 2,2-bis (3,4-di Carboxyphenyl) hexafluoropropane diacid anhydride 'to synthesize a polyimide precursor (weight average molecular weight · 14.50, number average molecular weight: 11,000), and then proceeded in the same manner as in Example 5. Evaluation of Photographic Characteristics. As a result, a good pattern having a resolution of 10 μm and a film residual rate of 92.0 / 0 in the unexposed portion can be obtained. The exposure dose at this time was 300 microjoules per square millimeter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration in the shape of the pattern was observed. Example 7 In Example 5, the protective group of a hydroxyl group was changed to an ethoxymethyl group to resynthesize a polyimide precursor, and evaluation of the light-sensitive properties was performed in the same manner as in Example 5. As a result, a good pattern having a resolution of 15 m and a film residual ratio of 90% on the unexposed portion can be obtained. The exposure dose at this time was 250 microjoules per square millimeter. Incidentally, after the exposure, even if the material is left to stand for 30 minutes to 2 hours before the printing step of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, no deterioration in the shape of the pattern is observed. Example 8 In Example 5, the compound that generates an acid by irradiating was changed to naphthalenedimethyliminotrifluoromethanesulfonic acid and a 238 wt% aqueous solution of tetramethylammonium hydroxide was used as a developer. Example 5 was evaluated in the same manner as in the photosensitivity characteristics. As a result, a resolution of 10 micrometers and 90% can be obtained. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 23 311837 554244 A7 V. Description of the invention (24) on the unexposed part A good pattern for the residual ratio of cyanide. The exposure dose at this time is micro-, ears / square millimeter. Incidentally, even after heating, even after heating (please read the precautions on the back before filling this page). Step 刖 Allow the material to stand for 30 minutes to 2 No deterioration in the shape of the pattern was observed even after 1 hour. Example 9 In Example 7, the compound that generates an acid by irradiation with radiation was changed to naphthalenedimethyliminotrifluoromethanesulfonic acid and 2.38% by weight of tetramethyl hydroxide was used. As a developer, ammonium was evaluated in the same manner as in Example 5. As a result, a good pattern having a resolution of 15 μm and a film residual ratio of 88% on the unexposed portion was obtained. The exposure at this time The dose was 200 microjoules per square millimeter. Incidentally, after exposure, even if the material was left to stand for 30 minutes to 2 hours before the heating step, no deterioration in the shape of the pattern was observed. Comparative Example 1 Same as Example 1 The procedure is carried out in a manner that does not protect the warp groups of the synthetic intermediates, and the evaluation of the photosensitivity characteristics is performed in the same manner as in the Example! Cooperatives PRINTED

As a result, a clear contrast could not be obtained in the coating film after development and the pattern was obtained by method A. …, Comparative Example 7 The procedure was performed in the same manner as in Example 1 but without adding a compound that generates an acid by irradiation and radiation, and then the same method as in the Example: Evaluation of light characteristics. As a result, even when the exposure material is immersed in the developer over a long period of time, the paper ruler has been used in the CNS A4 specification (210 X 297) _554244 A7 V. Description of the invention (25 ) It was also unable to dissolve the exposed part and the Japanese yen had peeled off due to the knife 1 mesh, so it was not possible to get tired. Comparative Example 3 (Please read the precautions on the back before filling out this page) * In accordance with the examples! The procedure was performed in the same manner, except that the protective group of each group was substituted with a third butoxycarbonyl group to synthesize a polyimide precursor, and then the evaluation of the photosensitive properties was performed in the same manner as in Example 1. When the heating step is performed within one minute of exposure, a good pattern having a resolution of 10 micrometers and a residual ratio of rhenium to the unexposed portion can be obtained. However, if the exposure material is left to stand for 20 minutes or more before the heating step, its surface is hardly dissolved in the developer, and a pattern cannot be obtained. Example 10 Poly-synthesis of oxazole precursor synthesis of the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Co-operative Society Printed in 50 g of Ν, Ν-dimethylacetamide (dmAc) Dissolved in 0.3 g of 4,4 -Dicarboxydiphenyl ether (OBBA). After adding 86 g of vaporized thionine under ice cooling, the resulting mixture is returned to room temperature and allowed to react for 2 hours. Then, 14.6 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 57 g of pyridine dissolved in 50 g of DMAc were added to the above mixture under ice-cooling, and this was further added. The mixture was stirred at room temperature for 30 minutes. This reaction mixture was added dropwise to distilled water, and the precipitate was collected by filtration, and dried under reduced pressure to obtain polyamide. The weight average molecular weight of this material was 14,500. Dissolve 10 grams of polyamidoamine in 50 grams of tetrahydrofuran, and add 28 grams of 2,3-dihydropyran and a catalytic amount of p-toluenesulfonic acid to the solution. The mixture was allowed to stir for an additional hour at room temperature. This reaction mixture was added dropwise to distilled water, and the precipitates formed were collected by filtration. The paper size was reduced to the Chinese National Standard (CNS) A4 (210 X 297 mm). 25 311837 Employees of the Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 554244 Α7-Β7 5. Description of the invention (%) Drying under pressure to obtain the polybenzoxazole precursor represented by formula (2). The substitution ratio of the tetrahydropyranyl group to the hydroxyl group of the obtained material was 58%. For details of the photosensitivity, add 100 parts by weight of the above-mentioned polybenzopyrene precursor to dimethoxyanthracene diphenyl moth gun as a compound that generates an acid by irradiation with radiation, and then dissolve the mixture in In 2-methoxyethanol. The above solution was spin-coated on a silicon wafer to form a coating film having a dry film thickness of 2 to 3 microns, and then subjected to i-line (365 nm) exposure through an interference filter using an ultra-high pressure mercury lamp. After the exposure, the exposed material was heated at 120 ° C for 5 minutes, and developed with a 238 wt% aqueous solution of tetramethylammonium hydroxide until the exposed Shi Xi wafer was exposed, and then washed with water. As a result, a good pattern having a resolution of 5 m and a film residual rate of 95% on the unexposed portion can be obtained. The exposure agent at this time was 200 microjoules per square meter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration in the shape of the pattern was observed. Example 11 In the same manner as in Example 10, except that the diferulic acid was changed to m-benzyl dicarboxylic acid, the same procedure was performed to obtain a polybenzopyrene salivary precursor, and the photosensitivity characteristics were performed in the same manner as in Example 10. evaluation of. As a result, a good pattern having a resolution of 6 m and a film residual rate of 92% on the unexposed portion can be obtained. The exposure dose at this time was 400 microjoules per square millimeter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration in the shape of the pattern was observed. Reinstallation of Polybenzoxazole Precursor -------- Order ----.------ f Please read the notes on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 size (210 X 297 mm) 26 311837 554244

5. Description of the invention (27) The weight average molecular weight is 15,000. Perform the same procedure as in Example 10 except that the dicarboxylic acid was changed to a mixture of terephthalic acid and isophthalic acid (molar ratio; i: υ) and copolymerized, and the same procedure was performed to obtain a polymer. The benzochrysene precursor was subjected to photosensitivity evaluation in the same manner as in Example 10. As a result, a good pattern having a resolution of 6 microns and a film residual rate of 93% on the unexposed portion was obtained. The exposure dose at this time 300 microjoules per square millimeter. Incidentally, after exposure, even if the material is left to stand for 30 minutes to 2 hours before the heating step, no deterioration in pattern shape is observed. The weight average of the polybenzoxazole precursor The molecular weight is 14,000. Example 13 In the same manner as in Example 10 except that the diamine was changed to 4,4, _diamino_3,3'-dihydroxybiphenyl, the same procedure was performed to obtain polybenzoxazole The precursor was evaluated in the same manner as in Example 10. As a result, a good pattern having a resolution of 8 μm and a film residual rate of 90% on the unexposed portion was obtained. The exposure dose at this time 400 microjoules / square Incidentally, no pattern shape deterioration was observed even after the material was left to stand for 30 minutes to 2 hours after the exposure after the exposure. The weight average molecular weight of the polybenzoxazole precursor was 2000 ( ). Example 14 In the same manner as in Example 10, but the compound that generates an acid by irradiation with radiation was changed to naphthalenedimethyliminotrifluoromethanesulfonic acid, and the same procedure was performed to obtain a polybenzoxazole precursor Then in the same way as in Example 10 (please read the notes on the back before filling this page). -------- Order ----.--- 1 | Line 1 Intellectual Property Bureau, Ministry of Economic Affairs The paper size printed by the employee consumer cooperative is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 27 311837 554244

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) Evaluation of the photosensitivity characteristics. As a result, a good pattern having a resolution of 6 m and a film residual rate of 95/0 in the unexposed portion can be obtained. The exposure dose at this time was 150 microjoules per square millimeter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration of the pattern shape was observed. Jfe Example 15 Synthesis of 5 polymoxazoxazole precursors; 50 g of N, N-dimethylacetamide (DMAc) was dissolved in 0.3 g of 4,4-monocarboxydiphenyl ether (BBA). After adding 86 g of vaporized thionine under ice cooling, the resulting mixture was returned to room temperature and allowed to react for 2 hours. Then 14.6 grams of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 57 grams of pyridine dissolved in 50 grams of DMAc were added to the above mixture under ice cooling. The mixture was stirred at room temperature for 30 minutes. This reaction mixture was added dropwise to distilled water, and the precipitate was collected by filtration, and dried under reduced pressure to obtain polyamide. The weight average molecular weight of this material was 14,500. Dissolve 10 g of the polyamine obtained above in 50 g of r.butyrolactone, and then add 1.96 g of second butyl monomethyl aerosol to this solution, and stir under ice cooling This mixture was for 3 hours. This reaction mixture was added dropwise to distilled water, and the formed precipitate was collected by filtration, and dried under reduced pressure to obtain a polybenzoxazole precursor represented by the formula (2). The substitution ratio of the third butyldimethylsilyl group to the hydroxyl group of the obtained material was 48/0. 1 Evaluation of light characteristics: Add 100 parts by weight of the aforementioned polybenzoxazole precursor to 15 parts by weight of dimethoxyanthracene diphenyl as a compound that generates an acid by irradiation of radiation (please read the precautions on the back first) (Fill in this page again) " ^^ 装 -------- Order ---- * --- 1 | line 'This paper size is applicable to China National Standard (CNS) A4 size ⑵G x 297 public) 28 311837 554244 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 311837 A7 V. Description of the invention (29) Basic iodine records, and then the mixture is dissolved in 2-methoxyethanol. 1. Apply spin coating to the above solution on a silicon wafer to form a coating layer with a dry thickness of 2 to 3 microns, and then use an ultra-high pressure mercury lamp to perform "line (365 nm) exposure through an interference filter. ~ Exposure Then, the exposed material was heated at 12 ° C for 5 minutes, and developed with a 2% tween% tetramethylammonium oxide aqueous solution until it was exposed on the exposed part of the dream wafer, and then washed with water. As a result, it was obtained Good pattern with a resolution of 8 microns and a film residual rate of 90 / 〇 on the unexposed parts. The exposure dose at this time is 250 microjoules per square millimeter. By the way, even after exposure, even before the heating step, This material was left to stand for 30 minutes to 2 hours without deterioration of the pattern shape. Μ Example 16 In the same manner as in Example 15 except that the dicarboxylic acid was changed to terephthalic acid and isophthalic acid (Mole Ratio: 1: mixture of υ and copolymerization, the same procedure was performed to obtain the polybenzoxazole precursor, and then the evaluation of the photosensitivity characteristics was performed in the same manner as in Example B. As a result, a resolution of 0 μm was obtained. Degrees and 88% of A good pattern of the film residual ratio of the exposed part at this time was an exposure dose of 300 microjoules per square millimeter. Incidentally, after the exposure, the pattern shape was not observed even after the material was allowed to stand for minutes to 2 hours before the heating step. The weight average molecular weight of the polybenzyl chelate precursor was 14.00. Paste Example 17 In the same manner as in Example 15 except that the protecting group of the hydroxyl group was changed to ethoxycene, and the same procedure was performed to Obtained the polybenzone chew precursor and then applied the cap national standard (C_NS) A4 size coffee x 297 publicly according to the actual scale. -------- ^ ------- 1 (please first Read the notes on the back and fill in this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 554244 A7 --- B7 V. Description of the invention (3〇) Example 15 The photosensitivity characteristics were evaluated in the same manner. Good resolution with micron resolution and 90% film residual rate in unexposed areas. The exposure dose at this time is 300 microjoules per square millimeter. Incidentally, after exposure, 'even before the heating step, No pattern was observed in this material after standing for 3 () minutes to 2 hours Example 18 In the same manner as in Example 15 except that the compound that generates an acid by irradiation with radiation was changed to naphthalenedimethyliminotrifluoromethanesulfonic acid, and the same procedure was performed to obtain polybenzoxamine The azole precursor was evaluated for photosensitivity in the same manner as in Example 5. As a result, a good pattern with a resolution of 8 microns and a film residual ratio of 90/0 on the unexposed portion was obtained. At this time The exposure dose was 150 microjoules per square millimeter. Incidentally, after the exposure, even if the material was left to stand for 30 minutes to 2 hours before the heating step, no deterioration in the shape of the pattern was observed. Example 19 Example 17 In the same way, but changing the compound that generates an acid by irradiation to naphthalenedimethyliminotrifluoromethanesulfonic acid, the same procedure is performed to obtain the polybenzoxazole precursor and then it is performed in the same manner as in Example IX. Evaluation of Photographic Characteristics. As a result, a good pattern having a resolution of 6 m and a film residual ratio of 92.0 / 0 in the unexposed portion can be obtained. The exposure dose at this time was 150 microjoules per square millimeter. Incidentally, even after the material was left to stand for 30 minutes to 2 hours after the exposure, no deterioration of the pattern shape was observed. Comparative Example 4 (Please read the Zhuyin on the back? Matters before filling out this page)

Install -------- Order ---- * ---- Line I

30 311837 554244 A7 V. Description of the invention (31) The procedure is performed in the same manner as in Example 10, but the warp group of the synthetic intermediate acetic acid vinegar is not protected, and then the photosensitive characteristics are performed in the same manner as in Example 10. evaluation of. As a result, a pattern obtained by a clear contrast method cannot be obtained in the coating film after development. Comparative Example 5 The procedure was performed in the same manner as in Example 10, but without adding a compound that generates an acid by two shots, and then the evaluation of the photosensitive characteristics was performed in the same manner as in Example 1G. As a result, even when the exposure material is immersed in the developer for a long time, the exposed portion cannot be dissolved and peeling occurs from the wafer to prevent patterning. Comparative Example 6 A procedure was performed in the same manner as in Example 10, except that the protective group was substituted with a third butoxy group to synthesize a polybenzonosaurus precursor, and the photosensitivity characteristics were evaluated in the same manner as in Example 10. . When the heating step was performed within 15 minutes of exposure, a good pattern having a resolution of 10 m and a film residual rate of 88% on the unexposed portion was obtained. However, if the exposure material is left to stand for 20 minutes or more before the heating step, its surface is hardly dissolved in the developer and a pattern cannot be obtained. The positive-type photosensitive resin composition of the present invention has excellent photosensitivity, resolution, and heat resistance. In addition, according to the method for producing a pattern according to the present invention, by using the above-mentioned resin composition, it is possible to obtain a paper with excellent sensitivity, resolution, and heat resistance. The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297). (Published) (Please read the note on the back? Matters before filling out this page)-Installed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed 554244 A7 _B7 V. Description of the invention (32) Good shape pattern. In addition, the electronic component of the present invention has high reliability because of its good shape and excellent characteristics. (Please read the precautions on the back before filling this page) '3 ^ Packing -------- Order ---- · 1 The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese national standard ( CNS) A4 size (210 X 297 mm) 32 311837

Claims (1)

554244 (February 17, 1992) A type of positive photosensitive resin composition including (A) /, a polyimide precursor having a structural unit represented by formula (1): (1) Each of R 4 represents a mono 4 benzyl group, an alkoxy group, or a alkoxide group which forms an acetal or a ketal, which can be converted into a hydrogen atom by decomposition of an acid] and ( B) A compound that generates an acid by irradiating radiation, and is 0.01 to 50 parts by weight for 100 parts by weight of (A). 2. The positive photosensitive resin composition according to item 1 of the patent application, wherein R1 in the formula (1) is an aromatic group having four bonded arms having an aproton-donating group or a fluorinated alkyl group. The tetravalent radical of the chemical structure of the substituted aromatic group. 3. The positive-type photosensitive resin composition according to item 1 of the patent application range, wherein R2 in the formula (1) is an aromatic group having four bonding arms or an arm having bonding arms and being adjacent to each other via an ether bond. A tetravalent group having a chemical structure of an aromatic group substituted with an aprotic electron donating group in the aromatic group. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs 4. H3 4. H3 The reaction product shown in the following formula (4) before the polyimide in the patent application: The positive photosensitive resin composition around item 1, Its precursor is a diamine compound of a tetracarboxylic dianhydride represented by the following formula (3) as a partial starting material. (3) [where R has the same meaning as defined in (1) Printed by the Committee of the Central Standards Bureau of the Ministry of Economic Affairs, the X Fortune Committee [In the formula, R2 has the same meaning as in formula]]. 5. The positive-type photosensitive resin composition according to item 4 of the scope of patent application, wherein the compound not represented by formula (3) is at least one type of compound selected from the following groups: 3,3 ', 4,4', _Diphenyl ether tetracarboxylic dianhydride, 込 'dimethoxy_2,3,5,6-benzyltetracarboxylic dianhydride, ^ rendi (trimethylsilyl) _ 2,3,5,6 • Dicarboxylic acid dianhydride, bis (3,4-dicarboxyphenoxy) phthalic anhydride, 1,3-bis (3,4-dicarboxyphenoxy) phthalic anhydride, 3,3,4 , 4 ,, _ monophenylmethane tetracarboxylic dianhydride, bis (3,4_dicarboxyphenoxy) dimethyl Shixiyuan dianhydride, bis (3,4-dicarboxyphenoxy) formaldehyde Aminoamine dianhydride, 4,4, bis (3,4-dicarboxyphenoxy) diphenylsalicylic anhydride, 2,2_ bis (3,4-dicarboxybenzyl) hexafluoropropane dianhydride and 2,2 _Bis (3,4_dicarboxyphenyl) -1,1,1_trifluoropropane dianhydride. 6. The photosensitive resin composition of the main part of the item j This paper is a national standard (nCNS) A4 size (2ΐ () χ. Public love)-H3 R2 in the compounds not included in formula (4) is selected from The following groups: Dixitong ^ _ 〇 Shibenfeng, Yiben Yafeng, diphenyl hexafluoropropane, and difluoromethyl). A positive-type photosensitive resin composition that declares item 1 of the patent scope, wherein the compound (B) generates an acid by irradiating radiation is selected from the group consisting of the following groups: v, v, diaryl, salt, and triaryl. Salt, dialkylbenzyl ethyl ketone sulfonium salt, diaryl iodonium salt, aryl diazonium salt, aromatic tetracarboxylic acid salt, aromatic continuous acid salt, nitrobenzyl vinegar, agranium N_ Oximidate sulfonate, aromatic sulfonamide and naphthoquinonediazide-4-sulfonate. A positive photosensitive resin composition including (A) a polyoxazole precursor having a structural unit represented by the following formula (2): Printed by the Shell and Welfare Committee of the Central Standards Bureau of the Ministry of Economics [wherein R5 represents a divalent organic group; R6 represents a tetravalent organic group, and each R7 represents a monovalent group, an alkoxy group, or A sintered sulphur group can be converted into a hydrogen atom by being decomposed by the action of an acid] a polyfluorene imine precursor or polyoxine having a group shown by -OR bonded to an aromatic ring in the molecule. Seated precursor, [wherein R represents a group constituting a monovalent acetal or ketal, a oxyalkyl group or an alkylsilyl group, which can be converted into a gas atom by the action of an acid], and (B) A compound that generates an acid by irradiating radiation, and (B) is from 0.001 to 50 parts by weight for 100 parts by weight of A). ___ This paper size ^ uses the Chinese National Standard (CNS) Α4 specification (210 x 297 public love Υ ^ 554244 H3 9 positive photosensitive resin composition in the 8th scope of the patent application, in which the poly: precursor is The reaction product of a dicarboxylic acid represented by the following formula (6) and a diamine compound not represented by the following formula (7) as part of the starting material: Renren "6", R5 < '0Η [wherein R5 and R5 in formula (2) has the same meaning] (7) [Wherein 'R6 has the same meaning as R6 in formula (2)]. 10. The positive-type photosensitive resin composition according to item 8 of the application, wherein (A) the polyoxazole precursor has a weight average molecular weight of 10,000 to 20,000. 11. The positive-type photosensitive resin composition according to item 8 of the application, wherein (B) the compound that generates an acid by irradiation is at least one selected from the group consisting of a diarylsulfonium salt and a triarylsulfonium salt , Dialkylacetophenone sulfonium salt, diaryl iron iodide salt, aryl diazonium salt, aromatic tetracarboxylic acid salt, aromatic sulfonate, nitrobenzyl ester, aromatic N_oxo Amino sulfonates, aromatic sulfonamides and naphthoquinonediazide_4_ sulfonates. 12.—A method for manufacturing a pattern composed of the positive photosensitive resin composition in the first or second scope of the patent application, including the following steps: coating the support as described in the first or second scope of the patent application The step of drying the positive photosensitive resin composition, the step of giving-the-dusting, the use of a water solution to make the exposure material visible. The paper size is in accordance with Chinese National Standard (CNS) A4 (210 x297). The Ministry of Economic Affairs Central Standards Bureau Shellfish Welfare Committee printed 554244 _H3_ shadow and the steps of heat treatment. 13. The method of claim 12 in which the pattern is applied as a surface protective film or an interlayer insulating film for electronic components. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm)